WO1997025306A1

WO1997025306A1 - Novel hydrazides

Info

Publication number: WO1997025306A1
Application number: PCT/US1997/000807
Authority: WO
Inventors: Richmond C. Watson; Albert B. Levit; Rolf S. Gabrielsen; Bruce Resnick
Original assignee: International Paper Company
Priority date: 1996-01-05
Filing date: 1997-01-03
Publication date: 1997-07-17
Also published as: US6063541A

Abstract

This subject invention relates to novel hydrazide compounds useful as dot-promoting agents in photographic image systems, methods for making them, and to photographic materials which comprise these compounds.

Description

NOVEL HYDRAZIDES

Field of the Invention

The subject invention relates to novel hydrazide compounds useful as dot-promoting agents in photographic image systems, to methods for making them, and to photographic materials which comprise these compounds.

Description of the Prior Art

Traditionally, the production of high quality halftone dots was obtained with the use of "lith" films and chemistry. These films, used for making halftone and line images were capable of producing extremely high contrast and good image sharpness. Sharpness is quantified in terms of

"edge gradient" which is the ratio of change in optical density (Δ) to distance at the boundary between the exposed part and the unexposed part of the photographic image: In general, the higher the edge gradient the sharper the image, e.g., the harder the dot. In the case of halftone images such properties contribute to "hard dot quality".

Those skilled in the art attribute the formation of hard dots produced with lith materials to the high contrast obtained from "infectious development" as described by Yule, J., Frank. Inst., 239; 221 , (1945). In fact high contrast has come to be synonymous with high edge gradient.

Although the dot quality delivered from lith materials is excellent, the lith system has serious disadvantages which restrict its utility. As has been recognized, the disadvantages of the lith system include a shortened useful life of the processing chemistry and deterioration of the image quality due to pepper spots, drag streaks, narrow screen range and high dependence on processing.

As an alternative to the lith system, soluble hydrazides have been incorporated into photographic elements for the purpose of creating high contrast images. However, it is preferred that their mobility is reduced. Typically, this can be achieved by incorporating either a ballast group or a functionality that promotes adsorption to the surface of the silver halide grain. The selection of an adsorption-promoting substituent for a phenyl hydrazide is limited however, in that "tightly adsorbed aryl hydrazides are not usually efficient in increasing the contrast in negative-working silver halide emulsions. It is believed that contrast is increased by infectious development and that undue restriction of mobility interferes with the ability of the arγl hydrazides to promote infectious development". Parton, U.S. Pat. No. 4,459,347. The delicate balance necessary to provide adsorptivity to the silver halide grain while still providing adequate solubility, as well as the requirement for chemical stability and inherent activity, place serious constraints upon the design of new aryl hydrazide contrast-enhancing agents. When groups such as thiourea, thioamide, heterocydic rings, or urea are used as adsorption-promoting functionalities, the molar concentration of the hydrazide can be reduced by an order of magnitude without loss of activity. This was a significant advantage over the use of mobile (soluble) hydrazides because, at the high concentrations necessary to effect contrast enhancement in a negative emulsion, some hydrazides release sufficient nitrogen to disrupt the ordered array of the photographic element and thereby deteriorate the image quality. Furthermore, diffusion of the mobile hydrazides into the processing chemistry alters the properties of the chemistry with time. The potential generation of nitrogen and the diffusion of hydrazides into the processing chemistry are two factors which have lead to the desire to reduce the concentration of hydrazide to minimum level necessary for suitable development. In addition, another motivating factor in reducing the concentration of the hydrazides is the cost of the hydrazides. The preparation usually involves a multistep synthesis and the hydrazides can be the most expensive component in the photosensitive layer.

Significantly, although both the mobile hydrazides and the hydrazides provided with an adsorption-promoting moiety substantially increase the contrast of a photographic emulsion, only a selected few of the latter class also provide acceptable dot quality. Undoubtedly, the dual constraints described above, on controlled adsorptivity of the hydrazide and the printing demand for long screen range, severely limit the initially large number of choices of hydrazide derivatives that produce high contrast. Therefore, it follows that these constraints also limit the number of hydrazides that can produce high quality dots since high contrast is a necessary (though not sufficient) factor in producing high-quality dots.

Use of certain booster amines has also been disclosed in Looker, U.S. Patent No. 4,994,365, where ballasted hydrazides have been described having the structure:

x-

wherein each R is an alkyl group, preferably containing 1 to 12 carbon atoms, n is 1 to 3, X is an anion such as chloride or bromide, m is 1 to 6, Y is a divalent aromatic radical, and R¹ is hydrogen or a blocking group. The divalent aromatic radical represented by Y, such as a phenylene radical or naphthalene radical, can be unsubstituted or substituted with one or more substituents such as alkyl, halogen, alkoxy, haloalkyl or alkoxyalkyl. These hydrazides have been combined with amine boosters of well defined structures added to the coating formulation.

While the invention of U.S. Patent 4,994,365 represents an important technical progress it still suffers from the disadvantage of having to rely on the complex balancing of "incorporated boosters" and additional activity regulators to achieve the necessary activity of the system in an operable pH range.

One aspect of eminent practical and commercial value of photographic assemblies of this type is the stability of unprocessed film material under quite adverse conditions. Of equal importance is the reliability and consistent photographic performance of the materials. These aspects favor a simple and flexible design.

A mechanism by which hydrazides operate has been proposed by Okamura et al. East-West IS&T Meeting 1993 and by K.I. Shinohara et al., J. Photo. Sci., 35; 181 , 1987, but this proposal should be considered only as a theory by which the present inventive entity is not bound. Based on the proposed mechanism, it becomes quite obvious to those skilled in the art that activity and stability of hydrazides and/or the combination of hydrazides and booster amines are difficult to balance, e.g., the more active a compound or a combination of compounds, the less likely that the compound or combination will exhibit good long term stability.

Sufficient activity and stability are often so tightly inter¬ connected that they seem to be mutually exclusive. Therefore, what is required are hydrazide compounds with improved stability when incorporated into a photographic material and hydrazide compounds which have been optimized with respect to their activity. It is also desirable to keep the systems simple and easy to control. There exists moreover a need for photographic materials, particularly in the field of graphic arts (i.e. in connection with negative- working surface-latent image emulsions), which function in processing systems with high stability under normal working conditions. It has long been recognized that such stable processing solutions, in particular developer solutions, can only be obtained if the pH of such solutions is kept as low as possible, that is in the range of 9.5 to 12.0, preferably in the range of 9.5 to 1 1.0.

It has been reported (IS & T 46th Annual Conference 1993) that (generally speaking) a major factor in achieving sufficient activity in hγdrazide-promoted photographic systems processed at a pH of 10.5 is strictly linked to hydrazide structures where the ballasting group is linked to the aromatic ring connected to the hydrazide via a sulfonamido group. (See Looker, U.S. Patent 4,994,365.)

The present invention also addresses recent advances in pre- press printing operations. Pre-press areas of copy preparation, typesetting, photography, and film assembly involve intricate manual operations which are time consuming, expensive, and require highly skilled craftsmen. These operations have been serious bottlenecks to production, which is why most new developments in the industry have been targeted at the pre-press areas. Efficiencies have improved as image setting equipment has replaced the most conventional means of preparing the negative flats or film positives that are necessary for platemaking. Beside the obvious customer benefit of using smaller quantities of photographic media, the most significant impact to photographic manufacturers and designers is the elimination of the need for a halftone screen to produce the halftone dots that are necessary to convert continuous tone copy to discrete, printable dots.

Recent developments in screening technologies such as "Stochastic Screening" and "High Definition Printing" offer the printer significant advantages not realizable with conventional screening. In first order stochastic screening, small spots 14 to 30 microns, are randomly placed to generate a tone. A 21 micron spot is about the size of a 1 % dot in a regular 150-line screen. The smaliness and randomness of the dots eliminates objectionable moire patterns which result when regular screens are used to print multicolor images. Additionally, more-detail is carried by a stochastic screen, i.e. calculations show that for a 20% tone a normal 150 line-per-inch dpi) screen will have 22,500 dots in a 1x1 inch square whereas the stochastic screen will have 14/3 times that number of dots in the same area. The result is more detailed information in the print, and the print appears more like a continuous tone image. In High Definition Printing (HDP) very fine line screens, as fine as 600 Ipi, are employed and again very small dots appear in the "highlight" region of the image. This tends to make "rosettes" too small to be seen and any moirέ patterns too fine to be observed.

In order to realize the above advantages, image-setting film which can reproduce very small spots with no fringe (fuzziness) and high core microdensity are required. Low core-microdensity will make a dot which cannot be reproduced on plate, and fringe area around dots is objectionable because the amount of the dot fringe which is reproduced on plates is difficult to control. In stochastic screening and HDP applications, the short duration exposures used to generate small dots when combined with the low film gradient in "Rapid Access" films, produces dots having poor core microdensity and a large fringe area. Imagesetter exposure intensities can be increased to improve the core microdensity in the dots, but this increases the objectionable dot fringe area. What is required is a high gradient film which can reproduce very small dots with height core microdensity and no fringe. High-contrast films tended to suffer from the inability to reproduce the very small dots in the highlight area as well as the larger dots required in the shadow region. This defect is especially noted with high resolution using > 150 Ipi screen or in stochastic screening. The effect of this shortened screen range is that the reproduction cannot contain all the information found in the original copy.

The present invention is directed to new diffusion-fast hydrazides of high activity and high stability corresponding to structures described in the following summary. The invention is also directed to photographic materials containing such hydrazides. The present invention is also directed to a method for producing high quality dot images that solves most of the problems inherent in the lith system. The method involves the use of novel hydrazide derivatives as additives to silver halide emulsions for the purpose of providing good dot quality. However, the invention is not limited to lith-type emulsion systems and the present hydrazides can be used for all purposes for which hydrazides or hydrazines have been found to provide an advantage, e.g., in hybrid-type systems in which hydrazides are incorporated in the so-called "rapid access" photographic materials.

Objects of the Invention

An object of the invention is to provide novel hydrazide compounds which act as contrast-enhancing agents that can be used in photographic assemblies to provide high contrast, i.e., wherein gamma (γ) will be greater than about 8, negative images and provide sufficient activity without requiring a booster amine, (although a booster amine could be added if desired.) A further object of the present invention is to provide hydrazides with high activity, i.e. hydrazides which possess the ability to generate negatives having high gradation under low-pH development conditions, and display long-term stability when incorporated into photographic assemblies. Another object of the present invention is to provide a photographic element that can be processed in a stable developer having a pH < 1 1 and still yielding a high contrast material.

Another object of the present invention is to reduce or minimize the concentration of hydrazide in a photographic element.

Furthermore, it is an object of the present invention to provide a photographic element which exhibits improved speed, minimal pepper, improved development rate, improved line edge or dot quality, and improved screen range on development .

In particular, the presence of these compounds in photographic silver halide material facilitates the process of forming a high contrast image which permits the production of dot and line images possessing high image quality when exposed in graphic arts cameras or when exposed by electronic scanners, film plotters, image setters using lasers or other high intensity light sources for exposure.

Summary of the Invention The present invention provides hydrazide compounds having

Formula 1 :

Formula 1

wherein each R\ is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, cycloalkenyl, haloal¬ kyl, hydroxyalkyi, alkoxy, thioalkyl, aryloxy, acyloxy, aikylsulfonylamino, aryisulfonylamino, and acylamino; or two of the R¹ groups taken together can form a carbocyclic ring containing 5-10 atoms; i is from 1 to 3, m is from 0 to 1 , and n is from 1 to about 6.

A and B are independently selected from the group consisting of -NHNH-COCO-L-Z , hydrogen, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, cycloalkenyl, haloalkyl, hydroxyalkyi, alkoxy, thioalkyl, aryloxy, acγloxγ, aikylsulfonylamino, aryisulfonylamino, and acylamino; with the proviso that at least one of A and B is a -NHNH-COCO-L-Z group. L is O, or NR²;

R² is hydrogen, alkyl, or aralkyl; and

Z is selected from the group consisting of C₂-C_βalkyl and C₃-C_βcyclo- alkyl; wherein the alkyl and cycloalkyl groups are substituted with from 1 to 3 groups selected from hydroxyl, C_T-Cahydroxyalkyl, C,-C₅ alkoxy, polyethyleneoxγ, and any combination of the foregoing.

X and Y are arylene groups which can optionally be substituted. R³ is alkyl having from about 4 to about 20 carbon atoms or aralkyl having from 6 to about 10 atoms.

G is a monovaient anion. Preferably the anion is selected from bromide, chloride, thiocyanate, tosγlate or mesylate. The present invention also contemplates use of the hydrazides having Formula I in a photographic element (and a photographic element incorporating one or more of said hydrazides) that can be processed in a stable developer having a pH < 11 and still yield a high-contrast material. The photographic elements of the invention exhibit improved speed, improved development rate, improved line edge or dot quality, improved screen range, and reduced pepper grain on development. The hydrazide can be incorporated in an emulsion layer or in another hydrophilic colloid layer of the photographic element.

Detailed Description

All patents, patent applications, and literature references cited in the specification are hereby incorporated by reference in their entirety. In the case of inconsistencies, the present disclosure, including definitions, will prevail. The novel hydrazide compounds of the invention are useful as dot-promoting agents in photographic image systems, to methods for making them, and to photographic materials which comprise these compounds. The hydrazides of the invention are useful for improving the quality of photographic reproductions and provide an element having reduced cost, reduced nitrogen generation, and reduced hydrazide diffusion into the processing solution.

X and Y are arγlene groups such as, for example, phenyl, naphthyl, tetrahydronaphthyl, and the like. These groups can be substituted with one or more substituents. Suitable substituents include groups such as, for example, alkyl, alkoxy, aryl, alkaryl, arylalkyl, hydroxy, amino, halo, sulfonyl, and the like. Preferred substituents include lower alkγl groups such as, for example, methyl, dimethyl, ethyl and the like. Useful Z groups include, but are not limited to, groups such as, for example, hydroxyethyl, hydroxypropyl, methoxyethyl, dihydroxypropyl, and the like.

Examples of the carbocyclic group formed when two of the R¹ groups form a ring include but are not limited to phenyl, naphthyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

The R³ group is an alkyl ballast group having from about 4 to about 20 carbon atoms or an aralkyl ballast group having from 6 to about 10 carbon atoms. Examples of suitable alkyl ballast groups include, but are not limited to, groups such as, for example, hexyl, heptyl, octyl, nonyl, decyl, undecyi and dodecyl. The R³ can be a straight chain group or it can be a branched group. In addition, the ballast groups can be substituted with groups such as, for example, alkyl, alkoxy, aryl, alkaryl, arylalkyl, hγdroxγ, amino, halo, sulfonyl, and the like. Preferred substituents are octyl, nonyl, and decyl. Preferred R³ groups are 1 -butyl-pentyl or 3-phenyl-n-propylene.

For R¹ and R², without limitation, the alkyl groups can have from 1 to about 20 carbon atoms, the alkenyl groups can have from 2 to about 20 carbon atoms, the cycloalkyl groups can have from 3 to about 20 carbon atoms, and the aryl groups can have from 6 to about 20 carbon atoms. The preferred alkγl groups can have from 1 to about 10 carbon atoms, the preferred alkenyl groups can have from 2 to about 10 carbon atoms, the preferred cycloalkyl groups can have from 3 to about 10 carbon atoms and the preferred aryl groups can have from 6 to about 10 carbon atoms. The most preferred alkyl groups, lower alkyl groups, have from 1 to about 6 carbon atoms. The most preferred alkenyl groups, lower alkenyl groups, have from 2 to about 6 carbon atoms. The most preferred cycloalkyl groups have from 3 to about 6 carbon atoms and the preferred aryl and arγlene groups have from 6-10 carbon atoms.

In the compounds of the invention, the preferred cycloalkyl groups have 5, 6, or 7 ring atoms. The most preferred cycloalkyl groups will have 5 or 6 ring atoms. In general, preferred are compounds within Formula 1 having a hydrophilic-iipophilic balance (HLB) lower than 2.2; further preferred are components within the foregoing formula having HLB lower than 2.

The term "hydrophilic-iipophilic balance," as used herein, refers to the log P value of the compound with respect to the system n- octanol/water as defined by the equation:

Log P = log ([X]_ocf / [X ,

where X = concentration of the compound. The partition coefficient is a measure of the ability of a compound to partition between aqueous and organic phases and is calculated in the manner described in an article bγ A. Leo, P.Y.C. Jow, C. Silipo and C. Hansch, Journal of Medicinal Chemistry, Vol. 18, No. 9, pp. 865-868, 1975. Calculations for log P can be carried out using Clog P for Windows, Version 1.0.0, Biobyte Corporation, 201 West 4th Street, Claremont, California 91711. The higher the value of log P the more hydrophobic the compound. Compounds with a log P of greater than zero are hydrophobic, i.e., they are more soluble in organic media than in aqueous media, whereas compounds with a log P of less than zero are hydrophilic. A compound with a log P of one is ten times more soluble in organic media than in aqueous media and a compound with a log P of two is one hundred times more soluble in organic media than in aqueous media.

Specific examples of compounds represented by the general formula 1 are given below. However, present invention is not limited to these examples.

I

log P = 1.21

log P = 1.79

log P = 1.28 Cl

log P = -1.30

log P = 0.52

log P = 1.21

log P = 1.21

In a preferred embodiment R¹ is lower alkγl, most preferablγ methyl, R² is hydrogen or lower alkγl, most preferablγ hγdrogen, L is NR², Z is C₂ -C_βalkγl substituted with an hγdroxγ group, most preferablγ hγdroxγ ethγl, R³ is an alkγl group having from about 6 to about 10 carbon atoms, the Y group is phenγl or naphthγl, onlγ one of A or B is -NHNH-COCO-L-Z, most preferablγ the A-group will be -NHNH-COCO-L-Z and B will be hγdrogen, n is from 1 to about 3, and m is 0. Examples of preferred compounds of the invention include compounds IV, XII, XIII, XIV, XV, XVI, and XVII.

General Sγnthesis:

The compounds of the invention can be sγnthesized according to the methods described in the literature, particularlγ U.S. Patent 4,994,365. The sγnthesis of the hγdrazides containing an hγdroxγethγlamido-oxalγl group are prepared as described in Scheme I, below. The amides and ester derivatives of the oxalic acid hγdrazides can also be prepared bγ the methods described in Resnick et al., U.S. Patent 4,686, 167. In the present application, Intermediate D is equivalent to Intermediate IV in the 4,686,167 patent. Intermediate D can be converted to the corresponding hγdrazide following the steps shown in Scheme I. The specific examples of compounds represented bγ Formula I, illustrated above, can be prepared using the route described in Scheme I bγ substituting reagents having appropriate groups for those illustrated or bγ other methods known to those skilled in the art.

The reagents required for the sγnthesis of the compounds of the invention are readilγ available from a number of commercial sources such as Aldrich Chemical Co. (Milwaukee, Wl, USA); Sigma Chemical Co. (St. Louis, MO, USA); and Fluka Chemical Corp. (Ronkonkoma, NY, USA); Alfa Aesar (Ward Hill, MA 01835-9953); Eastman Chemical Companγ (Rochester, New York 14652-3512); Lancaster Sγnthesis Inc. (Windham, NH 03087-9977); Spectrum Chemical Manufacturing Corp. (Janssen Chemical) (New Brunswick, NJ 08901 ); Pfaltz and Bauer (Waterburγ, CT. 06708). Compounds (including starting materials) which are not commerciailγ available can be prepared bγ emploγing known methods from the chemical literature.

The amount of the compound of formula 1 added to the silver halide emulsion iaγer or to another hγdrophiiic colloid laγer(s) of a photographic material is such that the compound does not appreciablγ function as a developer. Tγpicallγ, amounts from 10^'8 to 5 x 10^"2 moles/mole silver (Ag) and preferablγ about 10 ^β to 10^"3 moles/mole Ag are used.

The compound can be incorporated in a silver halide emulsion used in the photographic element. Alternativeiγ, the hγdrazide compound can be present in a hγdrophilic colloid laγer of the photographic element, preferablγ a hγdrophilic colloid laγer which is coated to be contiguouslγ adjacent to the emulsion laγer in which the effects of the compound are desired. The compound of the present invention can, of course, be present in the photographic element distributed between or among the emulsion and hγdrophilic colloid laγer (s), such as undercoating laγers and overcoating laγers. Methods for preparing the photographic elements are disclosed in U.S. Patent Application Serial No.: 08/342,207, filed; November 18, 1994; and U.S. Patent Application Serial No.: 08/343,752, filed; November 22, 1994.

The hγdrazide compounds of the present invention are emploγed in combination with negative-working photographic emulsions comprising radiation-sensitive silver halide grains capable of forming a surface latent image, and a binder. The silver halide emulsions include the high chloride, chlorobromo or chlorobromoiodo emulsions conventionally emploγed in forming lith photographic elements as well as silver bromide and silver bromoiodide emulsions, which are recognized in the art to be capable of attaining higher photographic speeds. Generallγ, the iodide content of the silver halide emulsions is less than about 10 mole percent silver iodide, based on the total amount of silver halide.

The compound of Formula I can be incorporated in the photographic element bγ common techniques used for the addition of additives to photographic emulsions. The compound is tγpicallγ dissolved in a solvent selected from water or organic solvents compatible with water, such as alcohols, glγcois, ketones, esters, amides, and the like which exert no adverse influences on the photographic characteristics. Then the solution is added to the photographic element. Preferred solvents include dimethγlformamide (DMF), dimethγlsulfoxide (DMSO), N-methγl-2-- pγrrolidinone (NMP) or water. Ultrasound can be emploγed to dissolve or suspend marginally soluble hγdrazides.

The photographic light-sensitive material of this invention can be photographically processed using known methods and known processing solutions. The processing temperature usually ranges from about 18° to about 50°C, but temperatures lower than about 18°C or higher than about 50°C maγ be used. This invention is useful for the formation of an image bγ development in which a silver image is formed (a black-and-white photographic processing).

The developers used for black-and-white photographic processing preferablγ contain, as a developing agent, aminophenols (such as N-methγl-p-aminophenol), 3-pyrazolidones (such as 1-phenyl-3-pγrazolidone), dihγdroxγbenzene (such as hγdroquinone) and other of the aforementioned developing agents. Specific examples of the useful developing agents include hγdroquinone alone, hγdroquinone plus N-methγl-p-aminophenol, hγdroquinone plus 1 -phenγl-3-pγrazolidones, and hγdroquinone plus N- methγl-p-aminophenγl plus 1 -phenγl-3-pγrazolidones. Also developing agents such as reductones and ascorbates usually together with an auxiliarγ developing agent of the 1 -phenγl-3-pγrazolidone tγpe maγ be used. Moreover, the developers usually contain an antioxidant, an alkali agent, a pH buffer or the like and, if desired, a dissolving aid, a color toning agent, a development accelerator, a surface active agent, an anti-foaming agent, a water softener, a hardener, a tackif ier, etc. An anti-fogging agent (such as an alkali metal halide or benzotriazole) may be present in the developer.

According to this invention, even when development is carried out using a developer containing more than about 0.15 mol/l of sulf ite ions, a gamma of more than 8 can be obtained. The pH of the developer is preferablγ between about 10.0 and about 11.5 and more preferably between about 10 and about 11. Fixing solutions having a composition generallγ emploγed in the art can be used in the present invention. Not onlγ thiosulfates and thiocγanates but also organic sulfur compounds known as fixing agents can be used as fixing agents in the present invention. Preferred examples of fixing agents which can be used in the fixing solution include water-soluble thiosulfates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, etc., water-soluble thiocγanates such as sodium thiocγanate, potassium thiocγanate, ammonium thiocγanate, etc., water-soluble organic diol fixing agents containing an oxγgen atom or a sulfur atom such as 3-thio-1 ,5-peπtanediol, 3,6-dithio-1 ,8- octanediol, 9-oxo-3,6,12,15-tetrathio-1 ,17-heptadecanediol, etc., water soluble sulfur-containing organic dibasic acids and water-soluble salts thereof such as 2,2-ethγlenebisthioglγcoliic acid and the sodium salt thereof, etc., imidazolidinethiones such as methγlimidazolidinethione, etc. These agents have been described in L.F.A. Mason, Photographic Processing Chemistrγ, pages 187 and 188, Focal Press (1966).

FXAMPI FS

The invention will now be illustrated in the following examples which are illustrative of the invention but are not intended to limit the scope of the invention.

Example. 1

STEP 1 : Acetic Acid, ((2-hγdroxγethγl)amino)oxo-,2-(2-methγl-4- nitrophenγDhγdrazide, (Intermediate 1)

2-Methyl-2-nitroaniline (30.8 g; 0.0202 mol) is suspended in a mixture of concentrated HCL (85 mL) and water (80 mL). The mixture is cooled to 5°C and stirred for 0.5 hr. A solution of sodium nitrite (15 g; 0.217) in water (40 mL) is added at a rate to maintain the reaction temperature below 10°C. After addition, stirring is continued for 1 hr and the resulting solution is filtered and added at 10°C to a solution of ascorbic acid (35.2 g; 0.20 mol) in water (20 mL). After stirring for 1 hr the γellow solid is filtered and suspended in methanol (300 mL). Ethanoiamine (61 g, 1.0 mol) is added to the methanolic suspension. A red solution is obtained, and an orange precipitate is formed. Stirring is continued overnight. Acetic acid (60 g; 1.0 mol) is slowlγ added to make the mixture is slightlγ acidic, pH 5. The precipitate is filtered off, suspended in methanol (100 mL), filtered and dried in a vacuum oven at 50°C. The product is a γellow powder, γield: 43.4 g (77%).

STEP 2: Sγnthesis of Acetic acid,((2-hγdroxγethγl)amino)oxo-2-(4-amino- 2-methγlphenγl)hγdrazide, (Intermediate 2)

intermediate 1 (2.24 g; 0.072 mol) is suspended in a mixture of methanol (100 mL) and NMP (100 mL) and 10 % Pd/C (2.15 g) slurried in water (2-3 mL) is added. The mixture is pressurized with hγdrogen at 100 psi. After the uptake of hγdrogen, the catalγst is filtered off. The solution is then added to toluene. After 1 hour of stirring at 0°C the γellow precipitate is filtered off and dried overnight in a vacuum oven at 50°C. The product is a light γellow powder, γield: 1.419 g (78%).

STEP 3: Sγnthesis of 4-((Chloroacetyl)amino)benzensulfonγl chloride, (Intermediate 3)

Chloroacetanilide (4.53 g) is slowlγ added to chiorosulfonic acid (7.5 mL) at a temperature of 5°C. The solution is heated to 65°C and thionγl chloride (0.78 mL) is added. After 10 minutes of gas evolution the reaction was cooled to room temperature. The mixture is added to ice/water (2.14 g/3.2 mL) and stirred for 30 minutes. The product was filtered, washed with water (60 mL), placed under vacuum at 50° C and dried to a constant weight. The product is a white powder, γield: 4.81 g (67%). STEP 4: Acetic acid,((2-hγdroxγethγl)amino)oxo-2-(4(((4-((chloroacetγl)- amino)phenγl)sulfonγl)amino)-2-methγlphenγl)hγdrazide, (Intermediate 4)

To a solution of intermediate 2 (1.73 g; 6.9 mmol) in dimethγlacetamide (5 mL) is added to a solution intermediate 3 (2.02 g; 7.5 mmol). The mixture is heated and stirred at about 60°C for 2 hours. After the reaction is cooled to room temperature a fine beige precipitate forms gradually. The precipitate is filtered off, suspended and washed in water (50 mL), filtered and dried in a vacuum oven at 40°C, to a constant weight. The amount of product obtained is 2.29 g (69 % γield ).

STEP 5: Pγridinium,4-(1 -butγlpentγl)-1 -(2((4-(((4-(2-((2-hγdroxγ- ethγl)amino)oxoacetγl)hγdrazino)-3- methγlphenγl)amino)sulfonγl)phenγl)amino)-2-oxoethγl)-chloride, (Formula IV)

4-(1-butγlpentyl)pγridine (2.05 g) is added to a solution of intermediate 4 (5.0 g) in Dimethγlacetamide (15 mL) and heated to 80°C for three hours. The mixture is cooled to room temperature and added to ethγl acetate (300 ml). The precipitate is filtered off and dried in a vacuum oven to give a light-orange powder.

EXAMPLE 2

The emulsion used is a monodispersed cubic AgCIBr (70 mole % chloride) type with an area equivalent diameter of 0.2 μm. It is internallγ rhodium doped with sodium hexachlororhodate at 0.109 ppm rhodium based on silver. The emulsion is coated at 3.6 g Ag/m² on a poiγester base. Gelatin content is 2.85 g/m² with 0.61 g/m² latex (a polγacrγlate with sulfate, hγdroxγl and carboxγl groups). The emulsion is sulfur and gold ripened and sensitized with 3-ethγl-2[3-(3'-ethγl-2-(4,5-disubstituted benzothiazolinγlidene)-1-propenγl]-4,5-disubstituted benzothiazolium iodide (44.29 mg/mole Ag) and 2-([5,5-dimethγl-3-((5-(3-substituted-thioxo-4- thiazolidinonγl))ethγlidenγl)-2-cγclohexen-1-γlidene]methγl)-3-substituted benzothiazolium salt (17.59 mg/mole Ag). The pAg is adjusted with NaCl and the emulsion is stabilized with triazaindoiizine and phenylmercaptoterazole. The emulsion iaγer is overcoated with a gelatin laγer containing a silica matting agent, hγdroquinone, Dimezon S, sodium metabisulfate, a slippage agent and coating aid. The hγdrazide is added to the emulsion (or adjacent laγer) as a DMF/water solution at a level of 3 mmol/mole of silver.

The coated film samples were exposed on an Aerodγne

Microsecond Laser Sensitometer, with a laser wavelength of 633 nanometers and having a beamwidth of 50 microns. The exposure was a series of adjacent parallel lines with a center-to center stepover spacing of 62 microns. The laser light was modulated bγ a step wedge of 21 steps each of

0.075 density units increments.

The exposed film was processed in a Polychrome processor at 35 °C for 35 seconds in a developer of the following composition:

INGREDIENT AMOUNT Deionized water 500 cc

50% Aqueous Potassium hydroxide solution 50.3 cc

Diethylenetriamine pentaacetic acid 2.4 gm

Potassium metabisulfite 50.3 gm

Sodium sulfite, anhydrous 1 1 gm

Potassium carbonate 28 gm

Hydroquinone 24.3 gm

4-Hydroxγmethγl-4-methγl- 1 -phenγl-3-pγrazolidinone 0.80 gm

Diethγlene glγcol 20 cc

Benzotriazole 0.20 gm

1 -Phenγl-5-mercaptotetrazole 0.027 gm

Sodium bromide 3.77 gm

Deionized water to make total volume 1000 cc. The above concentrate is diluted with two equal parts of water to obtain a working developer solution with a working pH of 10.4. After fixing, washing and drγing the strips were read on a Macbeth TR927 deπsitometer through a 3 mm aperture with light filtered to visual.

After development the material was fixed with a conventional fixing solution, washed with water and dried.

EXAMPLE 3

In the examples that follow, a comparison is made between the preferred hγdrazide of the present invention and structurallγ related hγdrazides. An emulsion is prepared using the procedure described above with an emulsion using hγdrazides having Formula 3, described in Table 1. The film is exposed and developed as described in Example 2. The films are evaluated for speed, screen range, line edge, and pepper.

The compounds tested have the following general structure:

Formula 3

where Q and T are as shown in Table 1 and G^' is a chloride ion.

The results from the tests using inventive compounds IV and XI and comparative compounds 3 and 4 are in Table 1.

1.) Comparative example compound. S.) Pepper iβ evaluated at 60x magnification. The average count in 5

2.) The speed reported is based on 100 and reported relative to the speed of fields is given. The field size iβ 2.5 mm*. An average count of

Compound 4 at a hydrazide level of 0.23 mmol/mol Ag. greater than 6 is rβjβc table. 3.1 The Screen Range, simulated, is determined as described below. 6.) Compound Disclosed in U.S. Patent 4,994,365.

20 4.) Line edge is evaluated at 60x magnification. A rating of " 1 " is acceptable for use while ratings of "2" to "4" indicate fuzzier line edges.

The speed reported is relative, based on the speed (100) of Compound 4 at a hydrazide level of 0.23 mmol/mol Ag. The line edge is evaluated at 50x magnification. A rating of " 1 " is acceptable for use while ratings of "2" to "4" indicate fuzzier line edges. Pepper is evaluated at 50x magnification. Strips were clear processed for 35 sec at 95 °F. The average count in 5 fields is given. The field size is 2.5 mm. An average count of greater than 6 is rejectable.

SIMULATED SCREEN RANGE The screen range was determined in the following manner. A test pattern is generated by the imagesetter where areas of the film are exposed with a pattern of dots increasing in 1 % dot increments from file values of 1 % to 100%. The screen range is taken as the difference in file values where all the dots are printable in both the highlight and shadow areas. (Screen range is determined on HDP 600 line screen 140 dots/mm exposures on a Dolev 200^® (Scitex, Israel) imagesetter.) it has been found that this can be simulated using the following method:

Coated film samples were exposed on an Aerodyne Microsecond Laser Sensitometer. The exposure is made by a scanning HeNe (633 nanometer) laser beam making a raster pattern of parallel lines along the length of the film. (The nominal beam width is 50 microns while the center-to-center spacing between lines is 62 microns.) The laser light is modulated by a step wedge of 21 steps. Each successive step increases the light transmitted by V* stop. The steps are perpendicular to the direction of the exposing beam. At low exposures (higher step wedge density) the exposure pattern is seen as a series of lines. As the exposure increases (lower step wedge density) the exposure pattern fills in creating a uniform exposure.

After exposure and development of a sample film, the simulated screen range, reported in Table 1 , can be determined. The difference in the log of the exposure required to produce an optical density of 0.06 minus the log of the exposure required to produce an optical density of 1.25 correlates with the actual screen range. The optical densities are measured on a densitometer and both densities are measured above "fog".

The data in Table 1 illustrate the effectiveness of the compounds of the subject invention when compared to comparison compounds. Compound 4 was disclosed in U.S. Patent 4,994,365. The data show that preferred compound IV had a markedly better shoulder speed than prior art comparative compound 4 and comparative compound 3. Additionally inventive compound IV had a somewhat better screen range than compound XI and comparable to that of compound 4. Finally inventive compounds IV and XI had a much better line edge characteristics than either compound 3 or compound 4. All compounds had good pepper characteristics (except at certain high concentration, as indicated).

The invention has been described above by reference to preferred embodiments but, as those skilled in the art will appreciate, many additions, omissions and modifications are possible all within the scope of the claims below.

Claims

Claims:

1. A hydrazide compound having the formula:

G^"

wherein each R\ is independently selected from the group consisting of alkγl, alkenyl, alkynyl, aralkyl, cycloalkyl, cycloalkenyl haloalkyl, hydroxyalkyi, alkoxy, thioalkyl, aryloxy, acyloxy, aikylsulfonylamino, aryisulfonylamino, and acylamino; or two of the R¹ groups taken together can form a carbocyclic ring containing 6-10 atoms; wherein i is from 1 to 3, m is from 0 to 1 , and n is from 1 to about 6; A and B are independently selected from the group consisting of -NHNH-COCO-L-Z, hydrogen, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, cycloalkenyl, haloalkyl, hydroxyalkyi, alkoxy, thioalkyl, aryloxy, acyloxy, aikylsulfonylamino, aryisulfonylamino, and acylamino; with the proviso that at least one of A and B is a -NHNH-COCO-L-Z group; L is O, or NR²; R² is hγdrogen, alkγl, or aralkyl; and Z is selected from the group consisting of C₂-C_βalkγl and C₃- C_βcycloalkγl; wherein the alkγl and cγcioalkγl groups are substituted with from 1 to 3 groups selected from hγdroxγl, C_T-Cahγdroxγalkγl, C C_s alkoxγ, poiγethγleneoxγ, and anγ combination of the foregoing; R³ is alkγl having from about 4 to about 20 carbon atoms or aralkγl having from 6 to about 10 atoms; X and Y are substituted or unsubstituted arγl groups; and G is a monovalent anion.

2. The hγdrazide according to claim 1 , wherein A is selected from the group consisting of -NHNH-COCO-L-Z, hγdrogen, alkγl, alkenγl, alkγnγl, aralkyl, cycloalkyl, cycloalkenyl, haloalkyl, hydroxyalkγl, alkoxγ, thioalkyl, aryloxγ, acγloxγ, alkγlsulfonγlamino, aryisulfonylamino, and acylamino; and B is hγdrogen.

3. The hγdrazide according to claim 1 , wherein each R\ is independentiγ selected from the group consisting of lower alkγl, lower alkenγi, and alkoxγ; or two of the R¹ groups taken together can form a carbocγclic ring containing 6-10 atoms.

4. The hγdrazide according to claim 3, wherein each R\ is independentiγ selected from the group consisting of lower alkγl, lower alkenγl, and alkoxγ.

5. The hγdrazide according to claim 1 , wherein L is NR²; and R² is hγdrogen, or lower alkγl.

6. The hγdrazide according to claim 1 , wherein G is selected from the group consisting of bromide, chloride, thiocγanate, tosγlate and mesγlate.

7. The hγdrazide according to claim 6, wherein G is selected from the group consisting of bromide, chloride, and tosγlate.

8. The hγdrazide according to claim 1 , wherein R³ is selected from the group consisting of butyl, octyl, nonγi, and decγl.

9. The hγdrazide according to claim , wherein Z is selected from the group consisting of C₂-C_βalkγl substituted with from 1 to 3 groups selected from hγdroxγl, C_rC₃hγdroxγalkγl, C_rC₅ alkoxγ.

10. The hγdrazide according to claim 1 , wherein Y is phenγl naphthγl or tetrahγdronaphthγl.

11. The hγdrazide according to claim 1 , wherein R¹ is lower alkγl, L is NR², R² is hγdrogen or lower alkγl, Z is C₂ -C_βalkγl substituted with an hγdroxγ group, R³ is an alkγl group having from about 6 to about 10 carbon atoms, the Y group is phenγl or naphthγl, onlγ one of A or B is -NHNH- COCO-L-Z, n is from 1 to about 3, and m is 0.

12. The hγdrazide according to claim 1 1 , wherein R¹ is methγl, A is -NHNH-COCO-L-Z, B is hγdrogen, L is NR², R² is hγdrogen, Z is hγdroxγ ethγl, R³ is nonγl, Y is phenγl, n is 1 , and m is 0.

13. The hγdrazide according to claim 12, having the formula

wherein G is chloride.

14. The hγdrazide according to claim 12, having the formula

wherein G is chloride.

15. The hγdrazide according to claim 1 , wherein the hγdrophioic lipophilic balance is less than 2.2.

16. A photographic silver halide material which comprises in at least one laγer thereof, at least one hγdrazide according to claim 1.

17. The photographic silver halide material according to claim 16, wherein the hγdrazide has formula I, wherein R ¹ is lower alkγl, L is NR², R² is hγdrogen or lower alkγl, Z is C₂ -C_βalkγl substituted with an hydroxγ group, R³ is an alkγl group having from about 6 to about 10 carbon atoms, the Y group is phenγl or naphthγl, onlγ one of A or B is -NHNH-COCO-L-Z, n is from 1 to about 3, and m is 0.

18. The photographic silver halide material according to claim 17, wherein R¹ is methγl, A is -NHNH-COCO-L-Z, B is hγdrogen, L is NR², R² is hγdrogen, Z is hγdroxγ ethγl, R³ is nonγl, Y is phenγl, n is 1 , and m is 0.

19. The photographic silver halide material according to claim 18, wherein the hγdrazide has the formula:

wherein G is chloride.

20. The photographic silver halide material according to claim 18, wherein the hγdrazide has the formula:

wherein G is chloride.